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室温下通过协同亲核 Ru-H 进攻途径用 trans-[Ru(NHC)H] 对氟代芳烃进行区域选择性催化加氢脱氟。

Room Temperature Regioselective Catalytic Hydrodefluorination of Fluoroarenes with trans-[Ru(NHC) H ] through a Concerted Nucleophilic Ru-H Attack Pathway.

机构信息

Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK.

Institute of Chemical Sciences, Heriot Watt University, Edinburgh, EH14 4AS, UK.

出版信息

Angew Chem Int Ed Engl. 2017 Feb 1;56(6):1515-1519. doi: 10.1002/anie.201610820. Epub 2017 Jan 9.

DOI:10.1002/anie.201610820
PMID:28067455
Abstract

The efficient and highly selective room temperature hydrodefluorination (HDF) of fluoroarenes by the trans-[Ru(IMe ) H ] catalyst, 3, is reported. Mechanistic studies show 3 acts directly in catalysis without any ligand dissociation and DFT calculations indicate a concerted nucleophilic attack mechanism. The calculations fully account for the observed selectivities which corroborate earlier predictions regarding the selectivity of HDF.

摘要

报道了通过反式-[Ru(IMe ) H ]催化剂 3，实现氟代芳烃在室温下高效、高选择性的加氢脱氟反应（HDF）。机理研究表明 3 在催化过程中直接作用，没有任何配体解离，DFT 计算表明该反应是协同亲核进攻机制。该计算完全解释了观察到的选择性，与之前关于 HDF 选择性的预测相符。

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